WO2016152885A1 - Film thermorétractable à base de polyester et corps d'emballage - Google Patents

Film thermorétractable à base de polyester et corps d'emballage Download PDF

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Publication number
WO2016152885A1
WO2016152885A1 PCT/JP2016/059096 JP2016059096W WO2016152885A1 WO 2016152885 A1 WO2016152885 A1 WO 2016152885A1 JP 2016059096 W JP2016059096 W JP 2016059096W WO 2016152885 A1 WO2016152885 A1 WO 2016152885A1
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Prior art keywords
film
heat
width
width direction
less
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PCT/JP2016/059096
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English (en)
Japanese (ja)
Inventor
雅幸 春田
多保田　規
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東洋紡株式会社
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Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to PL16768788T priority Critical patent/PL3275627T3/pl
Priority to KR1020177026993A priority patent/KR102408694B1/ko
Priority to EP16768788.8A priority patent/EP3275627B1/fr
Priority to JP2017508373A priority patent/JP6696501B2/ja
Priority to CN201680017031.5A priority patent/CN107405825B/zh
Priority to US15/559,738 priority patent/US9944012B2/en
Publication of WO2016152885A1 publication Critical patent/WO2016152885A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/08—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique transverse to the direction of feed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
    • B29C61/06—Making preforms having internal stresses, e.g. plastic memory
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
    • B29C63/0065—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65C—LABELLING OR TAGGING MACHINES, APPARATUS, OR PROCESSES
    • B65C3/00—Labelling other than flat surfaces
    • B65C3/26—Affixing labels to non-rigid containers, e.g. bottles made of polyethylene, boxes to be inflated by internal air pressure prior to labelling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D23/00—Details of bottles or jars not otherwise provided for
    • B65D23/08—Coverings or external coatings
    • B65D23/0842—Sheets or tubes applied around the bottle with or without subsequent folding operations
    • B65D23/0878—Shrunk on the bottle
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/744—Labels, badges, e.g. marker sleeves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2519/00—Labels, badges
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • the present invention relates to a heat-shrinkable polyester film suitable for heat-shrinkable label applications, and a package using the label.
  • polyester-based heat that has high heat resistance, easy incineration, and excellent solvent resistance for uses such as label packaging, cap seals, and integrated packaging that protect glass bottles or plastic bottles and display products.
  • Shrinkable films have been widely used as shrinkage labels, and the amount of use tends to increase with an increase in PET (polyethylene terephthalate) bottle containers and the like.
  • Patent Document 1 discloses a technology that suppresses the bowing phenomenon by changing the film temperature in the width direction of the biaxially stretched film in the width direction, although it is not a heat-shrinkable film.
  • Patent Document 2 also discloses a technique of heating so that the temperature distribution in the width direction is constant in order to obtain a laterally stretched film having no thickness unevenness in the width direction.
  • an object is to provide a heat-shrinkable polyester film that suppresses a difference in physical properties in the width direction even when the thickness is small.
  • the present invention that has solved the above problems is a heat-shrinkable polyester film characterized in that the film shrinkage direction is the main shrinkage direction and the following requirements (1) to (5) are satisfied.
  • the thickness of the film is 6 ⁇ m or more and 27 ⁇ m or less
  • the width 800 mm is divided into 8 samples, and the maximum value when the molecular orientation angles of the films are obtained for all the samples is 5 degrees or less
  • the width of 800 mm is divided into 8 samples, and all values of hot water shrinkage in the film width direction at 90 ° C. are 40% to 85% for all samples.
  • the width 800 mm was divided into 8 samples, and the difference between the maximum value and the minimum value when the hot water shrinkage rate in the film width direction at 90 ° C. was obtained for all samples was 2. %Less than, (5) In a film having a width of 800 mm or more, the width 800 mm is divided into four samples, and the difference between the maximum value and the minimum value when the maximum heat shrinkage stress in the film width direction at 90 ° C. is obtained for all the samples is Less than 0.3 MPa.
  • the absorbance ratio determined by 50mm pitch in the width direction 800 mm, 1340 cm -1 and the absorbance ratio of the 1410 cm -1 was determined by polarized ATR method for 17 points (1340cm -1 / 1410cm -1)
  • the difference between the maximum value and the minimum value is preferably 0.05 or less.
  • the thickness unevenness in the width direction obtained by the following formula is It is also preferably 1% or more and 13% or less.
  • Thickness variation (%) ⁇ (Tmax ⁇ Tmin) / Tave ⁇ ⁇ 100
  • the present invention also includes a package that is formed by heat shrinking by covering at least a part of the outer periphery of the package with a label obtained from the heat-shrinkable polyester film of the present invention.
  • the heat-shrinkable polyester film of the present invention is a thin film, the physical property difference in the width direction is suppressed to be small, so that the variation in the width direction of the heat-shrinkage behavior can also be suppressed to be small.
  • the polyester used in the heat-shrinkable polyester film of the present invention has an ethylene terephthalate unit as a main constituent component.
  • the ethylene terephthalate unit is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol% or more, in 100 mol% of the polyester structural unit.
  • dicarboxylic acid components constituting the polyester of the present invention include aromatic dicarboxylic acids such as isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid, fats such as adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid. And alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid.
  • the polyester does not contain a trivalent or higher polyvalent carboxylic acid (for example, trimellitic acid, pyromellitic acid, and anhydrides thereof).
  • a trivalent or higher polyvalent carboxylic acid for example, trimellitic acid, pyromellitic acid, and anhydrides thereof.
  • the diol component constituting the polyester includes ethylene glycol, 1,3-propanediol, 2,2-diethyl-1,3-propanediol, and 2-n-butyl-2-ethyl-1,3-propanediol.
  • Fats such as 2,2-isopropyl-1,3-propanediol, 2,2-di-n-butyl-1,3-propanediol, 1,4-butanediol, hexanediol, neopentyl glycol, hexanediol Diols, alicyclic diols such as 1,4-cyclohexanedimethanol, and aromatic diols such as bisphenol A.
  • cyclic diols such as 1,4-cyclohexanedimethanol and diols having 3 to 6 carbon atoms (for example, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, hexanediol, etc.) ) Is preferably used.
  • 1,4-butanediol or neopentyl glycol it is easy to obtain a polyester that satisfies the essential requirements of the present invention.
  • the total of amorphous components in 100 mol% of the polyhydric alcohol component and 100 mol% of the polyvalent carboxylic acid component (that is, in the total of 200 mol%) in all polyester resins is preferably 17 mol% or more. Is at least 18 mol%, more preferably at least 19 mol%, particularly preferably at least 20 mol%.
  • the upper limit of the total of amorphous components is not particularly limited, but is preferably 30 mol% or less.
  • the polyester should not contain a diol having 8 or more carbon atoms (for example, octanediol) or a trihydric or higher polyhydric alcohol (for example, trimethylolpropane, trimethylolethane, glycerin, diglycerin, etc.). Is preferred. In the heat-shrinkable polyester film obtained by using polyesters containing these diols or polyhydric alcohols, it is difficult to achieve a necessary high shrinkage rate. Further, it is also preferable that the polyester does not contain diethylene glycol, triethylene glycol, or polyethylene glycol as much as possible.
  • various additives as required, for example, waxes, antioxidants, antistatic agents, crystal nucleating agents, viscosity reducing agents, heat stability
  • An agent, a coloring pigment, an anti-coloring agent, an ultraviolet absorber and the like can be added.
  • fine particles as a lubricant for improving the workability (slidability) of the film.
  • the fine particles any one can be selected.
  • inorganic fine particles silica, alumina, titanium dioxide, calcium carbonate, kaolin, barium sulfate, etc.
  • organic fine particles for example, acrylic resin Examples thereof include particles, melamine resin particles, silicone resin particles, and crosslinked polystyrene particles.
  • the average particle size of the fine particles is in the range of 0.05 to 3.0 ⁇ m (when measured with a Coulter counter) and can be appropriately selected as necessary.
  • the above particles into the resin forming the heat-shrinkable polyester film for example, it can be added at any stage for producing the polyester resin, but it can be added at the esterification stage or transesterification reaction. After completion, it is preferable to add as a slurry dispersed in ethylene glycol or the like at a stage before the start of the polycondensation reaction, and proceed with the polycondensation reaction.
  • a method of blending a slurry of particles dispersed in ethylene glycol or water using a vented kneading extruder and a polyester resin material, or a dried particle and a polyester resin material using a kneading extruder It is also preferable to carry out by a method of blending and the like.
  • the heat-shrinkable polyester film of the present invention can be subjected to corona treatment, coating treatment, flame treatment or the like in order to improve the adhesion of the film surface.
  • the heat-shrinkable polyester film of the present invention includes a laminated polyester film having at least one polyester resin layer.
  • the polyester resin layer may be a polyester having the same composition or a polyester having a different composition.
  • stacked as another layer will not be specifically limited if it is a thermoplastic resin layer, However, From a price and a heat shrink property, it is preferable that it is a polystyrene-type resin layer.
  • thermoplastic resins include polystyrene having an atactic structure, styrene resins such as AS resin and ABS resin, polyester resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, nylon 6, nylon 66, nylon 12, nylon 4 And polyamide resins such as polyhexamethylene adipamide, and polyolefin resins such as polyethylene, polypropylene, and polybutene.
  • a rubbery copolymer containing a styrene compound as a constituent component is preferable, and examples thereof include a random, block or graft copolymer obtained by copolymerizing one or more of styrene and a rubber component.
  • examples of such rubbery copolymer include styrene-butadiene copolymer rubber, styrene-isoprene block copolymer, rubber obtained by hydrogenating a part or all of the butadiene portion, and methyl acrylate-butadiene-styrene.
  • Examples include copolymer rubber, acrylonitrile-butadiene-styrene copolymer rubber, acrylonitrile-alkyl acrylate-butadiene-styrene copolymer rubber, and methyl methacrylate-alkyl acrylate-butadiene-styrene copolymer rubber.
  • the rubbery copolymer containing the above-mentioned styrene compound as a constituent component has a styrene unit, and therefore has good dispersibility with respect to a polystyrene resin having a syndiotactic structure, and has an effect of improving plasticity with respect to the polystyrene resin. large.
  • the rubber-like copolymer which contains the above-mentioned styrene-type compound as the structural component can be used conveniently.
  • rubber components include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, ethylene-propylene copolymer rubber, urethane rubber, silicone rubber, acrylic rubber, polyether-ester rubber, polyester-ester rubber. Etc. can be used.
  • the weight average molecular weight of the polystyrene resin is preferably 10,000 or more, and more preferably 50,000 or more.
  • a film having a weight average molecular weight of less than 10,000 is not preferred because the strength and heat resistance of the film and the heat resistance are likely to be lowered.
  • the upper limit of the weight average molecular weight is not particularly limited, but if the weight average molecular weight exceeds 1,500,000, it may not be preferable because breakage may occur due to an increase in stretching tension.
  • Polystyrene resins of various grades are commercially available from various manufacturers, and commercially available resins may be used.
  • the heat-shrinkable polyester film of the present invention has a thickness of 6 ⁇ m to 27 ⁇ m. Since the object of the present invention is to thin the heat-shrinkable polyester film, it must be within this range. More preferably, they are 6 micrometers or more and 25 micrometers or less, More preferably, they are 6 micrometers or more and 20 micrometers or less.
  • the heat-shrinkable polyester film of the present invention preferably has a thickness unevenness of 13% or less in the width direction.
  • a film having a width of 800 mm or more and a film obtained by sampling a width of 800 mm so that a surplus is left and right evenly is used (hereinafter the same applies in this specification). Then, a sample having a width of 800 mm and a length of 40 mm is cut out, and the thickness is measured at a speed of 5 m / min with a load of measuring pressure 0.15 gf using “Film Synex” manufactured by Anritsu Corporation.
  • the average thickness value is Tave
  • the maximum value is Tmax
  • the minimum value is Tmin
  • the thickness unevenness exceeds 13%, the heat shrinkage behavior in the width direction also varies, which is not preferable.
  • the thickness unevenness is preferably as small as possible. However, since it is difficult to make it smaller than 1%, 1% is the lower limit.
  • the molecular orientation angle will be described.
  • the molecular orientation axis in the present invention is the most when viewed on the XY plane of the film when the longitudinal direction of the film is the X axis, the width direction of the film is the Y axis, and the thickness direction of the film is the Z axis direction.
  • the molecular orientation angle means an angle at which the molecular orientation axis when the molecular orientation axis is measured deviates from the film longitudinal direction or the film width direction.
  • the molecular orientation angle (angle in the molecular orientation axis direction) of the cut film sample is measured with a molecular orientation angle measuring device (MOA-6004) manufactured by Oji Scientific Instruments.
  • the molecular orientation angle is set to 0 degree in the longitudinal direction of the film.
  • the direction of the molecular orientation axis is smaller than 45 degrees with respect to the longitudinal direction, the difference from 0 degree is obtained, and from 90 degrees when larger than 45 degrees. Find the difference.
  • the heat-shrinkable polyester film of the present invention is obtained by dividing a width of 800 mm of a film having a width direction of 800 mm or more into 8 in the width direction, one side along the width direction is 10 cm, and one side along the direction perpendicular to the width direction.
  • a 10 cm square sample was cut out and immersed in hot water at 90 ° C. ⁇ 0.5 ° C. for 10 seconds without load, and the film was immediately immersed in water at 25 ° C. ⁇ 0.5 ° C. for 10 seconds.
  • the hot water shrinkage at 90 ° C. is preferably 45% or more, more preferably 50% or more.
  • contraction rate of the width direction in 90 degreeC exceeds 85% is low, the upper limit of hot water heat shrinkage
  • the heat-shrinkable polyester film of the present invention has a hot water shrinkage rate of 90 ° C. in the longitudinal direction of the film (direction perpendicular to the main shrinkage direction) measured in the same manner as described above of ⁇ 5% to 12%. Preferably there is. If the hot water shrinkage in the longitudinal direction at 90 ° C. is less than ⁇ 5%, the amount of film stretched by heating is too large, and a good shrink appearance cannot be obtained when used as a bottle label. On the other hand, when the hot water heat shrinkage rate in the longitudinal direction at 90 ° C. exceeds 12%, the label after heat shrinkage becomes shorter (label height decreases), and the label area becomes smaller.
  • the difference between the maximum value and the minimum value of the hot water shrinkage rate in the width direction at 90 ° C. is 8% or less among eight samples obtained by dividing the width of 800 mm into eight in the width direction. It is also important. If this difference exceeds 2%, the hot water shrinkage in the width direction varies, which is not preferable.
  • the heat-shrinkable polyester film of the present invention has a difference between the maximum value and the minimum value when the maximum shrinkage stress in the film width direction is measured in hot air at 90 ° C. for a sample obtained by dividing the width of 800 mm into four in the width direction. It is also important that the pressure be less than 0.3 MPa. If this difference is 0.3 MPa or more, the thermal shrinkage behavior in the width direction varies, which is not preferable.
  • the maximum shrinkage stress in the film width direction in hot air at 90 ° C. is preferably 2 MPa or more and 14 MPa or less. When the maximum shrinkage stress at 90 ° C.
  • the maximum shrinkage stress at 90 ° C. is more preferably 4 MPa or more, and further preferably 5 MPa or more. On the other hand, if the maximum shrinkage stress at 90 ° C. exceeds 14 MPa, the label after heat shrinkage tends to be distorted, which is not preferable.
  • the maximum shrinkage stress at 90 ° C. is more preferably 13.5 MPa or less, and further preferably 13 MPa or less.
  • the length of the sample for measuring the maximum shrinkage stress is 100 mm.
  • Heat-shrinkable polyester film of the present invention (measured in 17 points) for the film width direction 800mm measured absorbance ratio at 50mm pitch, absorbance ratio of 1340 cm -1 and 1410 cm -1 was determined by polarized ATR method (1340 cm - and the difference between the maximum value and the minimum value in 1/1410 cm -1) measurement of 17 points of 0.05 or less.
  • the above absorbance ratio represents a trans conformation ratio of molecular orientation.
  • the trans conformation is considered to represent the entangled state of the molecular chain, and the entangled state of the molecular chain is high when the trans conformation ratio is high.
  • polyester using an amorphous monomer as a raw material
  • the ease of contraction changes depending on the structure of the molecular chain (rotational isomer length)
  • the entanglement of molecular chains that are easy to contract is high
  • By applying sufficient heat to loosen the entanglement it is considered that the entanglement of the molecular chain is relaxed and reduced (change in the molecular chain is increased), and the shrinkage rate is also increased.
  • the difference between the maximum value and the minimum value of the absorbance ratio exceeds 0.05, it means that the heat shrinkage behavior in the width direction varies, which is not preferable.
  • the absorbance ratio itself in the width direction in each measurement at 17 locations is preferably 0.65 to 1.0.
  • the absorbance ratio is more preferably 0.67 or more, and further preferably 0.69 or more.
  • the absorbance ratio in the film width direction exceeds 1.0, the molecular orientation becomes too high, the shrinkage speed becomes fast (it does not shrink gently), and wrinkles and distortions are likely to occur in the shrinked label.
  • the absorbance ratio in the width direction is more preferably 0.98 or less, and even more preferably 0.96 or less.
  • the polarized ATR method is a method for analyzing the molecular orientation of the sample surface (about several ⁇ m), in the laminated polyester film, the absorbance ratio in the outermost polyester layer is within the above numerical range. Is preferred. The method for measuring the absorbance ratio will be described later.
  • the heat-shrinkable polyester film of the present invention is formed by melting and extruding the above-described polyester raw material with an extruder to form an unstretched film, and then heat-treating the unstretched film by uniaxial stretching by a predetermined method shown below. Can be obtained.
  • a plurality of extruders, feed blocks, and multi-manifolds may be used.
  • the polyester can be obtained by polycondensing the above-described preferred dicarboxylic acid component and diol component by a known method. Usually, two or more kinds of chip-like polyester are mixed and used as a raw material for the film. In the case of stacking, a plurality of extruders may be used.
  • the polyester raw material is preferably dried using a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer. After the polyester raw material is dried in such a manner, it is melted at a temperature of 200 to 300 ° C. and extruded into a film using an extruder. In extruding, any existing method such as a T-die method or a tubular method can be employed.
  • an unstretched film can be obtained by quenching the extruded sheet-like molten resin.
  • a method of rapidly cooling the molten resin a method of obtaining a substantially unoriented resin sheet by casting the molten resin from a die onto a rotating drum and rapidly solidifying it can be suitably employed.
  • the obtained unstretched film is preheated at 80 to 120 ° C., preferably 90 to 110 ° C., if necessary, and then 3.0 times or more with a tenter or the like in the transverse direction (direction perpendicular to the extrusion direction), preferably Stretch from 3.5 times to 7 times.
  • the stretching temperature is 65 ° C. or higher and 100 ° C. or lower, preferably 70 ° C. or higher and 95 ° C. or lower. It is not always necessary to perform longitudinal stretching before and after lateral stretching, but longitudinal stretching may be performed as necessary.
  • both ends of the film are heated with an infrared ceramic heater so that the temperature is equal to or higher than the temperature at the center of the film. More preferably, the temperature is 1 to 4 ° C. higher than the part.
  • both ends of the film are held by clips, so that the thickness of the end becomes thicker than the center.
  • the temperature at the end of the film during stretching is lower than that at the center and the stretching stress increases, so the so-called bowing phenomenon increases and the difference in physical properties in the film width direction increases.
  • the output of the infrared ceramic heater during transverse stretching so that the film temperature at the end after stretching is equal to or higher than the center.
  • the production speed when the thickness of the whole film becomes thin, it is necessary to increase the production speed in order to maintain the production amount.
  • the production rate is increased, the residence time in the tenter is shortened and the temperature difference in the width direction is generally increased.
  • the deformation speed at the time of transverse stretching also increases, the stretching stress increases, the bowing phenomenon increases, and the physical property difference in the film width direction increases. Therefore, it is preferable to keep the stretching stress at the end portion low.
  • heat treatment is performed to relieve the tension state of the stretched film, and is effective in adjusting the heat shrinkage rate at the temperature during the heat treatment and reducing the natural shrinkage rate.
  • heat treatment when the stretched film is heated in the heat treatment zone, there is a problem that a bowing phenomenon occurs and physical properties in the width direction are deteriorated (reference: molding processing, 4 (5), 312 (1992), plastics. Published by Japan Society for Molding and Processing).
  • the inventors examined the suppression of the Boeing phenomenon.
  • the infrared ceramic heater is preferably installed in the heat treatment process in addition to the above-described transverse stretching process. Heating with a ceramic heater is preferably about 5 to 20% of the entire width from the edge of the film. Further, it is preferable to heat with an infrared ceramic heater so that the end portion is 1 to 4 ° C. higher than the central portion at the temperature in the film width direction after the heat treatment step. Thereby, the heat-shrinkable polyester film of the present invention is obtained.
  • the heat-shrinkable polyester film of the present invention can be labeled by a conventionally known method.
  • a heat-shrinkable polyester film cut to a desired width is appropriately printed, and the right and left ends of the film are overlapped and bonded together by solvent adhesion or the like to produce a tube film.
  • This tube film is cut into an appropriate length to obtain a tube-shaped label.
  • the organic solvent for adhesion cyclic ethers such as 1,3-dioxolane or tetrahydrofuran are preferable.
  • aromatic hydrocarbons such as benzene, toluene, xylene and trimethylbenzene
  • halogenated hydrocarbons such as methylene chloride and chloroform
  • phenols such as phenol, and mixtures thereof
  • a perforated tunnel (steam tunnel) of the type in which perforation is formed on the above-mentioned label by a known method and then covered with a PET bottle, and the PET bottle is placed on a belt conveyor or the like, or hot air is blown The inside of the shrinking tunnel (hot air tunnel).
  • the label is attached to a bottle container such as a plastic bottle by the thermal contraction of the label when passing through these tunnels.
  • the package of the present invention is formed by heat-shrinking a label having a perforation or a notch obtained from the heat-shrinkable polyester film of the present invention on at least a part of the outer periphery of the package object.
  • the packaging object include PET bottles for beverages, various bottles, cans, plastic containers such as confectionery and lunch boxes, paper boxes, and the like.
  • the label is heat-shrinked by about 5 to 70% and adhered to the package.
  • printing may be given to the label coat
  • Hot shrinkage hot water heat shrinkage
  • a width of 800 mm or more of a film having a width direction of 800 mm or more is divided into 8 in the width direction, a side sample along the width direction is 10 cm, and a side sample perpendicular to the width direction is 10 cm on a square sample, Immerse it in hot water at 90 ° C ⁇ 0.5 ° C for 10 seconds under no load, and immediately immerse the film in water at 25 ° C ⁇ 0.5 ° C for 10 seconds. 1 was used to determine the heat shrinkage (that is, hot water shrinkage at 90 ° C.)
  • Hot water shrinkage rate ⁇ (length before shrinkage ⁇ length after shrinkage) / length before shrinkage ⁇ ⁇ 100 (%)
  • Chip A was obtained by a conventional method.
  • Chip B polyethylene terephthalate
  • chip C polybutylene terephthalate
  • NPG is neopentyl glycol.
  • the intrinsic viscosities of chips A, B, and C were 0.72 dl / g, 0.70 dl / g, and 1.15 dl / g, respectively.
  • Tables 1 and 2 show the contents of the raw material chips used in the examples and comparative examples, and the resin compositions and production conditions of the films in the examples and comparative examples, respectively.
  • Example 6 it is a single layer type film by a blend polymer, and Example 6 is a three-kind five-layer type film of X / Y / Z / Y / X.
  • Example 1 The above-described polyester A, polyester B, and polyester C were mixed at a mass ratio of 70:20:10 and charged into an extruder. This mixed resin was melted at 280 ° C., extruded from a T-die, wound on a rotating metal roll cooled to a surface temperature of 30 ° C., and rapidly cooled to obtain an unstretched film having a thickness of 72 ⁇ m. At this time, the take-up speed of the unstretched film (the rotation speed of the metal roll) was about 20 m / min. Moreover, Tg of the unstretched film was 67 degreeC.
  • FIG. 1 is an explanatory view of the transverse stretching machine as viewed from above.
  • the black square is an infrared ceramic heater.
  • the set temperature was 95 ° C.
  • An infrared ceramic heater is placed as shown in FIG. 1 (this arrangement is an example), and the output is adjusted to 60%, so that the set temperature of the transverse stretching temperature is 75 ° C. while heating both ends of the film.
  • the film was stretched 4 times.
  • the heat treatment step was performed at 85 ° C. for 8 seconds in a tension state. At this time, the infrared heater in the heat treatment zone was not used.
  • Example 2 A film having a thickness of 14.4 ⁇ m was produced in the same manner as in Example 1 except that the transverse draw ratio was 5 times and the set temperature of the heat treatment step was 80 ° C. The evaluation results are shown in Table 3.
  • Example 3 Except for mixing polyester A and polyester B at a mass ratio of 60:40, setting the preheating process temperature to 100 ° C, setting the transverse stretching temperature to 80 ° C, and increasing the output of the infrared ceramic heater to 90%.
  • a film having a thickness of 18 ⁇ m was produced.
  • the Tg of the unstretched film was 75 ° C.
  • the evaluation results are shown in Table 3.
  • Example 4 Example except that the speed of the cooling roll after melt extrusion was increased to 45 m / min, the thickness of the unstretched film was 32 ⁇ m, the preheating step was set to 90 ° C., and the transverse stretching was set to 72 ° C. In the same manner as in Example 1, a film having a thickness of 8 ⁇ m was produced. However, the passage time of the heat treatment step was shortened from 8 seconds to 3.6 seconds. The evaluation results are shown in Table 3.
  • Example 5 A film having a thickness of 8 ⁇ m was produced in the same manner as in Example 4 except that the setting temperature for the preheating step was 95 ° C., the setting temperature for the transverse stretching was 75 ° C., and the setting temperature for the heat treatment step was 95 ° C.
  • the evaluation results are shown in Table 3.
  • Example 6 Using a co-extrusion method, core layer forming resin, skin layer forming resin, and adhesive layer forming resin are melt-extruded from separate extruders (first to third extruders) and dies (T-die). By laminating inside and winding around a rotating metal roll cooled to 30 ° C. by air knife method and quenching, the thickness is 72 ⁇ m. Adhesive layers) were laminated, and unstretched films (polystyrene-based resin laminated sheets) having a structure in which skin layers were laminated on the outer sides of the intermediate layers were obtained. The method for forming each layer of the unstretched film (steps until melt extrusion) is as follows.
  • the first layer, the second layer, the third layer, the fourth layer, and the fifth layer are referred to in order from the front and back of the polystyrene-based mixed resin laminated sheet (that is, the surface of the fifth layer is a metal Roll contact surface).
  • the take-up speed of the unstretched film was about 20 m / min.
  • each of the above-mentioned chips A and B is preliminarily dried using a blender device, and then 95 parts by mass of the preliminarily dried chip A and 5 masses of the chip B The parts were mixed with a blender and then continuously fed to the hopper directly above the first extruder with a fixed screw feeder.
  • the supplied mixture of chips A and B was melt-extruded at 280 ° C. from the T-die of the single-screw type first extruder (laminated on the outer side of the intermediate layer laminated on the outer side of the core layer). Melt extruded).
  • a helical type and parallel type gear pump was interposed between the extruder and the T die.
  • the pre-dried chip D is placed in a hopper directly above the second extruder. It supplied continuously with the fixed amount screw feeder. Then, the supplied chip D was melt-extruded from a T-die of a single-screw second extruder (melt-extruded so as to be laminated on the outer sides of the core layer). The temperature of the second extruder was adjusted to 200 ° C. Similarly to the extrusion by the first extruder, a helical type and parallel type gear pump was interposed between the extruder and the T die in order to stabilize the extrusion from the T die.
  • the temperature of the third extruder was also adjusted to 200 ° C. Also, like the extrusion by the first extruder and the extrusion by the second extruder, in order to stabilize the extrusion from the T die, a helical type and parallel type gear pump was interposed between the extruder and the T die. .
  • the discharge amount of the first to third extruders in the formation of the unstretched film is as follows: first layer / second layer / third layer / fourth layer / fifth layer.
  • the thickness ratio was adjusted to 20/3/26/3/20.
  • a film having a thickness of 18 ⁇ m was produced from the obtained unstretched film in the same manner as in Example 1 except that the preset temperature in the preheating step was 100 ° C. and the preset temperature in the stretch step was 80 ° C.
  • the evaluation results are shown in Table 3.
  • Example 7 The thickness is the same as in Example 1 except that the output of the infrared heater in the transverse stretching process is 0%, the set temperature in the heat treatment process is 84 ° C., and the output of the infrared heater in the heat treatment process is 60%. An 18 ⁇ m film was produced. The evaluation results are shown in Table 3.
  • Example 8 A film having a thickness of 18 ⁇ m was produced in the same manner as in Example 7 except that the output of the infrared heater in the heat treatment step was 90%. The evaluation results are shown in Table 3.
  • Example 9 A film having a thickness of 18 ⁇ m was produced in the same manner as in Example 1 except that the set temperature in the heat treatment step was 84 ° C. and the output of the infrared heater in the heat treatment step was 50%. The evaluation results are shown in Table 3.
  • Comparative Example 1 The speed of the cooling roll after melt extrusion is reduced to 9 m / min, the thickness of the unstretched film is 160 ⁇ m, preheating is performed at 100 ° C., transverse stretching is performed at 78 ° C., and the output of the infrared ceramic heater is 0%. A 40 ⁇ m thick film was produced in the same manner as in Example 1 except that. However, the passage time of the heat treatment process was increased from 8 seconds to 17.8 seconds. The evaluation results are shown in Table 3.
  • Comparative Example 2 Example 1 except that the speed of the cooling roll after melt extrusion was increased to 45 m / min, the thickness of the unstretched film was 32 ⁇ m, preheating was performed at 90 ° C., and the output of the infrared ceramic heater was 0%. A film having a thickness of 8 ⁇ m was produced in the same manner. However, the passage time of the heat treatment step was shortened from 8 seconds to 3.6 seconds. The evaluation results are shown in Table 3.
  • Comparative Example 3 A film having a thickness of 18 ⁇ m was produced in the same manner as in Example 3 except that the transverse stretching was performed at 70 ° C. and the output of the infrared ceramic heater was 0%. The evaluation results are shown in Table 3.
  • Comparative Example 4 A film having a thickness of 8 ⁇ m was produced in the same manner as in Comparative Example 2 except that the output of the infrared ceramic heater in the transverse stretching process was 30% and the set temperature in the heat treatment process was 95 ° C. The evaluation results are shown in Table 3.
  • the heat-shrinkable polyester film of the present invention has a small variation in the heat shrinkage behavior in the width direction while being a thin film. Therefore, in label applications such as bottles processed industrially continuously, most labels can have a beautiful appearance regardless of the position of the film used.

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Abstract

La présente invention concerne un film thermorétractable à base de polyester pour lequel une différence de propriété physique dans la direction de la largeur est maintenue petite, même lorsque le film est mince, le film présentant la direction principale de retrait dans la direction de la largeur du film et étant caractérisé en ce qu'il satisfait aux conditions (1)-(5) suivantes : (1) l'épaisseur du film se situe dans la plage de 6-27 µm ; (2) l'angle maximal d'orientation moléculaire du film est de 5° ou moins ; (3) le taux de retrait à l'eau chaude dans le sens de la largeur du film à 90°C est de 40-85 % ; (4) la différence entre les valeurs maximale et minimale du taux de retrait à l'eau chaude dans le sens de la largeur du film à 90°C est de 2 % ou moins ; et (5) la différence entre les valeurs maximale et minimale lorsqu'on trouve la contrainte de retrait thermique maximale dans le sens de la largeur du film à 90°C est inférieure à 0,3 MPa.
PCT/JP2016/059096 2015-03-25 2016-03-23 Film thermorétractable à base de polyester et corps d'emballage WO2016152885A1 (fr)

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PL16768788T PL3275627T3 (pl) 2015-03-25 2016-03-23 Termokurczliwa folia poliestrowa i opakowanie
KR1020177026993A KR102408694B1 (ko) 2015-03-25 2016-03-23 열수축성 폴리에스테르계 필름 및 포장체
EP16768788.8A EP3275627B1 (fr) 2015-03-25 2016-03-23 Film de polyester thermoretractable et emballage
JP2017508373A JP6696501B2 (ja) 2015-03-25 2016-03-23 熱収縮性ポリエステル系フィルムおよび包装体
CN201680017031.5A CN107405825B (zh) 2015-03-25 2016-03-23 热收缩性聚酯系薄膜及包装体
US15/559,738 US9944012B2 (en) 2015-03-25 2016-03-23 Heat-shrinkable polyester film and package

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JP6036832B2 (ja) * 2013-06-11 2016-11-30 東洋紡株式会社 熱収縮性ポリエステル系フィルムおよび包装体
KR102444943B1 (ko) * 2016-05-31 2022-09-20 다이니폰 인사츠 가부시키가이샤 전지용 포장 재료, 그의 제조 방법, 전지 및 폴리에스테르 필름
US11453209B2 (en) 2018-07-25 2022-09-27 Gunze Limited Heat-shrinking multilayer film and heat-shrinking label
CN112789156A (zh) 2018-10-08 2021-05-11 伊士曼化工公司 由树脂共混物制成的可结晶可收缩膜和可热成形片材

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EP3275627B1 (fr) 2019-12-25
TWI692504B (zh) 2020-05-01
EP3275627A1 (fr) 2018-01-31
US9944012B2 (en) 2018-04-17
PL3275627T3 (pl) 2020-06-29
JP6696501B2 (ja) 2020-05-20
JPWO2016152885A1 (ja) 2018-01-25
TW201700600A (zh) 2017-01-01
CN107405825A (zh) 2017-11-28
KR20170129783A (ko) 2017-11-27
CN107405825B (zh) 2019-10-08
KR102408694B1 (ko) 2022-06-14
EP3275627A4 (fr) 2018-10-24
US20180043607A1 (en) 2018-02-15

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